Use of reactive dyes for dyeing hair

ABSTRACT

Reactive dyes of the formula I                    
     where 
     a is 1 or 2, 
     b is 0 or 1, 
     Y is vinyl or a radical of the formula C 2 H 4 Q, where Q is an alkali-detachable group, 
     L 3  is a direct bond or a bridge member of the formula CO—NH—M 1 , where M 1  is C 2 -C 6 -alkylene with or without interruption by 1 or 2 unadjacent oxygen atoms, imino or C 1 -C 4 -alkylimino groups, 
     A 1  is hydroxysulfonyl or a radical of the formula SO 2 Y, 
     A 2  is hydrogen, hydroxysulfonyl, methoxy, chlorine, bromine or carboxyl, 
     W is either in case 1) the radical of a coupling component, of a monoazo dye or additionally, when b=0, of a disazo dye, which may each bear further fiber-reactive groups, or 
      in case 2) the radical of a chromophore which optionally has further reactive groups, 
     L 1  and L 2  are each a bridge member, 
     are useful for hair dyeing and for use in cosmetic preparations for dyeing hair.

The present invention relates to the use of reactive dyes of the formulaI

where

a is 1 or 2,

b is 0 or 1,

Y is vinyl or a radical of the formula C₂H₄Q, where Q is analkali-detachable group,

L³ is a direct bond or a bridge member of the formula CO—NH—M¹, where M¹is C₂-C₆-alkylene with or without interruption by 1 or 2 unadjacentoxygen atoms, imino or C₁-C₄-alkylimino groups,

A¹ is hydroxysulfonyl or a radical of the formula SO₂Y,

A² is hydrogen, hydroxysulfonyl, methoxy, chlorine, bromine or carboxyl,

W is either in case 1) the radical of a coupling component, of a monoazodye or additionally, when b=0, of a disazo dye, which may each bearfurther fiber-reactive groups, or

 in case 2) the radical of a chromophore which optionally has furtherfiber-reactive groups and is derived from an optionally metallized mono-or disazo dye, from a triphendioxazine, from an anthraquinone, from ametallized formazan or from a metallized phthalocyanine,

L¹ is either in case 1) an azo bridge or

 in case 2) a bridge member of the formula O₂S—NZ¹, OC—NZ¹, Z¹N—SO₂,Z¹N—CO, Z¹N—CO—NZ², NZ¹ or

where M² is a direct bond or methylene, Z¹ and Z² are each independentlyof the other hydrogen, C₁-C₆-alkyl or phenyl and X is fluorine, chlorineor bromine, amino, C₁-C₆-alkylamino with or without interruption by 1 or2 unadjacent oxygen atoms, imino or C₁-C₄-alkylimino groups and with orwithout hydroxyl substitution, N-pyrrolidinyl, N-piperidinyl,N-morpholinyl, N-piperazinyl or N—(C₁-C₄)-alkylpiperazinyl, or NZ¹ orNz² each also represent 1,4-piperazinediyl,

L² is a radical of the formula

where Z³, Z⁴, Z⁵ and Z⁶ are each independently of the others hydrogen,C₁-C₆-alkyl or phenyl, L⁴ is C₂-C₈-alkylene or unsubstituted orC₁-C₄-alkyl-, C₁-C₄-alkoxy- or hydroxysulfonyl-substituted phenylene,and X is in each case as defined above,

for dyeing hair, to a method for hair dyeing and to cosmeticpreparations for dyeing hair.

The use of reactive dyes falling within the general formula I for dyeingnitrogenous fibers such as wool is known, for example, from U.S. Pat.No. 4,066,638, EP-A-107 614, EP-A-559 617, DE-A-3,441,273 andDE-A-2,154,942. Depending on the dyeing process, dyeing prescriptionsfor cotton and wool involve a pH of 10-12, temperatures within the rangefrom 60 to 80° C. and treatment times around the 10 hour mark.

U.S. Pat. No. 4,102,641 discloses the use of halotriazinyl reactive dyesfor dyeing hair.

JP-A-75 025 529 describes dye formulations for use as hair dyes. Thereactive dyes used therein are based on p-sulfatoethylsulfonylaniline asdiazo component and fiber-reactive radical. Therefore dyeing with thesedyes requires relatively long treatment times.

It is an object of the present invention to provide dyes for dyeing hairunder benign dyeing conditions, such as mild pH, short treatment timesand low temperatures.

We have found that this object is achieved by the use of reactive dyesof the general formula I for dyeing human hair.

The reactive dyes of the formula I are each indicated in the form of thefree acid. It will be appreciated that the use of their physiologicallyacceptable salts is likewise encompassed by the present invention.

Suitable cations are derived from metal or ammonium ions. Metal ions areespecially lithium, sodium or potassium ions. Ammonium ions for thepurposes of the present invention are substituted or unsubstitutedammonium cations. Examples of substituted ammonium cations aremonoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammoniumcations or those cations derived from nitrogenous five- or six-memberedsaturated heterocycles, such as pyrrolidinium, piperidinium,morpholinium, piperazinium or N-alkylpiperazinium cations or theirN-monoalkyl- or N,N-dialkyl-substituted products. Alkyl is generallystraight-chain or branched C₁-C₂₀-alkyl, which may be substituted by 1or 2 hydroxyl groups and/or interrupted by from 1 to 4 oxygen atoms inether function.

In general, all alkyl and alkylene groups mentioned above and appearingin the formulae which follow may be straight-chain or branched.

Substituted alkyl radicals preferably contain, unless otherwise stated,1, 2 or 3 substituents, especially 1 or 2 substituents, in any desiredposition.

Z¹, Z², Z³, Z⁴, Z⁵ and Z⁶ are each for example methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

M¹ and L⁴ are each for example (CH₂)₂, (CH₂)₃, (CH₂)₄, CH(CH₃)CH₂,CH(CH₃)CH(CH₃), (CH₂)₅, (CH₂)₆.

M¹ may also be (CH₂)₂O(CH₂)₂, (CH₂)₃O(CH₂)₂, (CH₂)₂O(CH₂)₂O(CH₂)₂,(CH₂)₂NH(CH₂)₂, (CH₂)₃NH(CH₂)₂, (CH₂)₂NH(CH₂)₂NH(CH₂)₂,

L⁴ may also be for example (CH₂)₇, (CH₂)₈, 1,2-, 1,3- or 1,4-phenylene,which may be mono- or disubstituted by methyl, methoxy orhydroxysulfonyl.

X is methylamino, ethylamino, propylamino, isopropylamino, butylamino,isobutylamino, tert-butylamino, pentylamino, hexylamino,hydroxymethylamino, 2-hydroxyethylamino, 2- or 3-hydroxypropylamino, 2-or 4-hydroxybutylamino, methoxymethylamino, 2-methoxyethylamino, 2- or3-methoxypropylamino, 2- or 4-methoxybutylamino, ethoxymethylamino,ethoxyethylamino, ethoxypropylamino, ethoxybutylamino, propoxyethylaminoor propoxypropylamino.

Q is an alkali-detachable group. Such groups include for examplechlorine, bromine, C₁-C₄-alkylsulfonyl, phenylsulfonyl, OSO₃H, SSO₃H,OP(O)(OH)₂, C₁-C₄-alkylsulfonyloxy, phenylsulfonyloxy,C₁-C₄-alkanoyloxy, C₁-C₄-dialkylamino or a radical of the formula

where Z⁷, Z⁸ and Z⁹ are identical or different and each is independentlyof the others C₁-C₄-alkyl or benzyl and An^(⊖) is in each case oneequivalent of an anion. Suitable anions include for example fluoride,chloride, bromide, iodide, mono-, di- or trichloroacetate,methanesulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.

When a is 2, the radicals

can be identical or different.

When b is 1, the radicals W can likewise be identical or different.

The fiber-reactive group of the formula II

where A¹, A², L³ and Y are each as defined above, will hereinafter bereferred to as “E”.

Preference for use in the dyeing of hair is given to reactive dyes ofthe formula I where L³ is a direct bond.

Preference is further given to the use of reactive dyes of the formula Iwhere A¹ is hydroxysulfonyl.

Preference is likewise given to the use of reactive dyes of the formulaI where L³ is a direct bond and A¹ is a radical of the formula SO₂Y.

Preference for the use in dyeing hair is also given to reactive dyes ofthe formula I where A² is hydrogen or especially hydroxysulfonyl.

Preference for use in the dyeing of hair is further given to reactivedyes of the formula I where L¹ is an azo bridge.

Preference is also given to the use of reactive dyes of the formula Iwhere L¹ is a bridge member of the formula

and X is as defined above.

Particular preference is given to the use of reactive dyes of theformula I where the hydroxysulfonyl radical is disposed ortho or para toL¹ and the fiber-reactive radical is disposed para or ortho to L¹ orpara to the hydroxysulfonyl radical.

Reactive dyes of the formula I whose fiber-reactive radical conforms tothe formula II a-g

are very particularly preferred for dyeing hair.

Preference for use in the dying of hair is further given to reactivedyes of the formula I where Y is a radical of the formula —C₂H₄SSO₃H,—C₂H₄Cl, —C₂H₄OCOCH₃ and particularly —C₂H₄OSO₃H or especially vinyl.

Preference is also given to the use of dyes of the formula I where thesubstituents are selected from a combination of the above-recitedpreferred substituents.

The SO₂Y radicals are additively reacting fiber-reactive radicals, whichare distinguished from the substitutively reacting fiber-reactiveradicals.

Substitutive reaction of the fiber-reactive group with the relevantnucleophilic groups (HNuc-) in the substrates, for example with theamino groups of hair, means that the leaving groups or atoms (eg.fluorine or chlorine) in the fiber-reactive radical are substitutivelyreplaced by the amino groups of the hair as per the following scheme:

Additive reaction of the fiber-reactive group with the relevant groupsin the substrates, for example with the amino groups of hair, means thatthe amino groups of the hair undergo an addition reaction with thefiber-reactive group as per the following scheme:

Examples of substitutively reacting fiber-reactive radicals arehalogen-substituted radicals derived from 1,3,5-triazine, quinoxaline,phthalazine, pyrimidine, pyridazine or 2-alkylsulfonylbenzothiazole asheterocyclic parent species.

The following heterocyclic radicals are particularly suitable:

where Z² is as defined above,

Hal is fluorine, chlorine or bromine,

U¹ is hydrogen or nitro, and

U² and U³ are independently hydrogen or C₁-C₆-alkyl with or withoutsubstitution by hydroxyl, halogen, cyano, hydroxysulfonyl or a radicalof the formula —SO₂—Y, where Y is as defined above, and in each casewith or without interruption by 1 or 2 oxygen atoms in ether function,imino or C₁-C₄-alkylimino groups, or

U² and U³ are together with the linking nitrogen atom pyrrolidinyl,piperidinyl, morpholinyl, piperazinyl or N—(C₁-C₄-alkyl)piperazinyl, or

U² can also be a radical of the formula

and the rings B¹ and B² may each be mono- or disubstituted byhydroxysulfonyl and/or benzofused, and the ring B² may independently bemono- or disubstituted by chlorine, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy,cyano, carboxyl, acetylamino, hydroxysulfonylmethyl or a radical of theformula CH₂—SO₂—Y, SO₂—Y, NH—CO—Y or NU²—CO—NU²—L⁵—SO₂—Y, where Y and U²are each as defined above and L⁵ is C₂-C₆-alkylene with or withoutsubstitution by hydroxyl, chlorine, cyano, carboxyl,C₁-C₄-alkoxycarbonyl, C₁-C₄-alkanoyloxy or sulfato and with or withoutinterruption by 1 or 2 oxygen atoms in ether function or imino orC₁-C₄-alkylimino groups.

Examples of additively reacting fiber-reactive radicals are acryloyl,mono-, di- or trichloroacryloyl, mono-, di- or tribromoacryloyl,—CO—CCl═CH—COOH, —CO—CH═CCl—COOH, 2-chloropropionyl,1,2-dichloropropionyl, 1,2-dibromopropionyl, 3-phenylsulfonylpropionyl,3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl,2-chloro-2,3,3-trifluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylcarbonyl,2,2,3,3-tetrafluorocyclobutylsulfonyl,2-(2,2,3,3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or 1- or2-arylsulfonylacryloyl, such as 1- or 2-methylsulfonylacryloyl, or aradical of the formula SO₂—Y, CONH—L⁶—SO₂—Y or NHCONH—L⁶—SO₂—Y, where Yis as defined above and L⁶ is C₁-C₄-alkylene or phenylene.

W in the formula I is in case 1) for example the radical of a couplingcomponent, of a monoazo dye or additionally, when b=0, of a disazo dyewhich optionally has additional fiber-reactive groups. In this case, thefiber-reactive group E is linked to the radical W via an azo bridge(—N═N—). If W is a monoazo dye, its coupling component will be linked tothe fiber-reactive group E via an azo bridge. Correspondingly, if W is adisazo dye, coupling takes place onto its diazo component.

Reactive dyes of this class suitable for hair dyeing conform for exampleto the formula IIIa, IIIb, IIIc or IIId

(E—N═N—)_(a)K  (IIIa)

E—N═N—K—N═N—D  (IIIb)

E—N═N—(K—N═N—D)—N═N—D  (IIIc)

(E—N═N—)₂(—K—N═N—D)  (IIId)

where K is the radical of a coupling component, D is the radical of adiazo component, a is 1 or 2 and E is as defined above. If, in theformulae IIIa and IIId, the radical E occurs twice (a=2), then theradicals E can be either identical or different from each other.Similarly, in the formula IIIc, the radicals D can be identical ordifferent.

Useful dyes of this class for hair dyeing are for example water-solubleazo dyes, especially monoazo dyes of the formula IIIa (a=1), disazo dyesof the formula IIIa (a=2) or IIIb or trisazo dyes of the formula IIIc orIIId which have hydroxysulfonyl and/or carboxyl groups.

Important coupling components HK are derived for example from compoundsof the benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole orN-arylacetoacetamide series.

Important diazo components D—NH₂ are derived for example from compoundsof the aniline or aminonaphthalene series. It is possible to use them ascoupling components at the same time. So the terms diazo and couplingcomponent are not mandatory for the preparative process, but merelyreflect one possible process.

W in the formula I is further for example, in case 2), the optionallymetallized radical of an azo dye. Suitable azo dyes from which suchradicals W are derived are known per se and have been described in largenumbers, for example in K. Venkataraman, The Chemistry of SyntheticDyes, Vol. VI, Academic Press, New York, London, 1972. Suitable azo dyesconform for example to the formula IV

D—N═N—K(—N═N—D)₁  (IV),

where D is the radical of a diazo component, K is the radical of acoupling component and 1 is 0 or 1 and where, when 1 is 1, the radicalsD are identical or different from each other.

Useful dyes from which the radical W is derived include for examplewater-soluble azo dyes, especially monoazo dyes of the formula IV (l=0)which may have hydroxysulfonyl and/or carboxyl groups.

The radical W is preferably derived from unmetallized azo dyes,especially from those containing sulfonic acid and/or carboxyl groups,of which those having from 1 to 6 sulfonic acid groups are to beparticularly emphasized.

Important azo dyes from which the radical W is derived not only incase 1) but also in case 2) are for example those of thephenyl-azo-naphthalene, phenyl-azo-1-phenylpyrazol-5-one,phenyl-azo-benzene, naphthyl-azo-benzene, phenyl-azo-aminonaphthalene,naphthyl-azo-naphthalene, naphthyl-azo-1-phenylpyrazol-5-one,phenyl-azo-pyridone, phenyl-azo-aminopyridine, naphthyl-azo-pyridone,naphthyl-azo-aminopyridine or stilbyl-azo-benzene series.

Radicals D of diazo components of the aniline or aminonaphthalene serieswhich do not bear fiber-reactive groups are derived for example fromamines of the formulae Va-f

where

m is 0, 1, 2 or 3,

p is 0, 1 or 2,

q is 0 or 1,

F¹ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, acetyl, cyano, carboxyl,hydroxysulfonyl, C₁-C₄-alkoxycarbonyl, hydroxyl, carbamoyl, mono- ordi-(C₁-C₄)alkylcarbamoyl, fluorine, chlorine, bromine ortrifluoromethyl,

F² is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, cyano, carboxyl,hydroxysulfonyl, acetylamino, C₁-C₄-alkoxycarbonyl, carbamoyl, mono- ordi-(C₁-C₄)alkylcarbamoyl, fluorine, chlorine, nitro, sulfamoyl,C₁-C₄-mono- or dialkylsulfamoyl, C₁-C₄-alkylsulfonyl, phenylsulfonyl orphenoxy and

L⁷ is a direct bond, oxygen,-sulfur or a radical of the formula —NHCO—,—NHCONH—, —CONH—, —CO—, —NHSO₂—, —SO₂NH—, —SO₂—, —CH═CH—, —CH₂—CH₂—,—CH₂—, —NH—, or —N═N—.

Preference is given to those components in which F¹ is hydrogen, methyl,methoxy, carboxyl, hydroxysulfonyl, hydroxyl or chlorine, F² ishydrogen, methyl, methoxy, carboxyl, hydroxysulfonyl, acetylamino orchlorine, and L⁷ is a radical of the formula —CO—, —SO₂—, —CH═CH—,—CH₂—CH₂—, —CH₂— or —N═N—.

Aromatic amines suitable for use as diazo components and conforming tothe formula Va, Vb, Vc or Vd include for example aniline,2-methoxyaniline, 2-methylaniline, 4-chloro-2-aminoanisole,4-methylaniline, 4-methoxyaniline, 2-methoxy-5-methylaniline,2,5-dimethoxyaniline, 2,5-dimethylaniline, 2,4-dimethylaniline,2,5-diethoxyaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline,2,5-dichloroaniline, 4-chloro-2-nitroaniline, 4-chloro-2-methylaniline,3-chloro-2-methylaniline, 4-chloro-2-aminotoluene,4-phenylsulfonylaniline, 2-ethoxy-1-naphthylamine, 1-naphthylamine,2-naphthylamine, 4-methylsulfonylaniline,2,4-dichloroaniline-5-carboxylic acid, 2-aminobenzoic acid,4-aminobenzoic acid, 3-aminobenzoic acid, 3-chloroaniline-6-carboxylicacid, aniline-2- or -3- or -4-sulfonic acid, aniline-2,5-disulfonicacid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid,2-aminotoluene-4-sulfonic acid, 2-aminoanisole-4-sulfonic acid,2-aminoanisole-5-sulfonic acid, 2-ethoxyaniline-5-sulfonic acid,2-ethoxyaniline-4-sulfonic acid, 4-hydroxysulfonyl-2-aminobenzoic acid,2,5-dimethoxyaniline-4-sulfonic acid, 2,4-dimethoxyaniline-5-sulfonicacid, 2-methoxy-5-methylaniline-4-sulfonic acid,4-aminoanisole-3-sulfonic acid, 4-aminotoluene-3-sulfonic acid,2-aminotoluene-5-sulfonic acid, 2-chloroaniline-4-sulfonic acid,2-chloroaniline-5-sulfonic acid, 2-bromoaniline-4-sulfonic acid,2,6-dichloroaniline-4-sulfonic acid, 2,6-dimethylaniline-3- or-4-sulfonic acid, 3-acetylaminoaniline-6-sulfonic acid,4-acetylaminoaniline-2-sulfonic acid, 1-aminonaphthalene-4-sulfonicacid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-5-sulfonicacid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonicacid, 1-aminonaphthalene-3,7-disulfonic acid,1-aminonaphthalene-3,6,8-trisulfonic acid,1-aminonaphthalene-4,6,8-trisulfonic acid, 2-naphthylamine-5- or -6- or-8-sulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonic acid,2-aminonaphthalene-6,8-disulfonic acid,2-aminonaphthalene-1,6-disulfonic acid, 2-aminonaphthalene-1-sulfonicacid, 2-aminonaphthalene-1,5-disulfonic acid,2-aminonaphthalene-3,6-disulfonic acid,2-aminonaphthalene-4,8-disulfonic acid, 2-aminophenol-4-sulfonic acid,2-aminophenol-5-sulfonic acid, 3-aminophenol-6-sulfonic acid,1-hydroxy-2-aminonaphthalene-5,8- or -4,6-disulfonic acid,4-aminodiphenylamine, 4-amino-4′-methoxydiphenylamine,4-amino-4′-methoxydiphenylamine-3-sulfonic acid,4-(2′-methylphenylazo)-2-methylaniline, 4-aminoazobenzene,4′-nitrophenylazo-1-aminonaphthalene,4-(6′-hydroxysulfonylnaphthylazo)-1-aminonaphthalene,4-(2′,5′-dihydroxysulfonylphenylazo)-1-aminonaphthalene,4′-amino-3′-methyl-3-nitrobenzophenone, 4-aminobenzophenone,4-(4′-aminophenylazo)benzenesulfonic acid,4-(4′-amino-3′-methoxyphenylazo)benzenesulfonic acid or2-ethoxy-1-naphthylamine-6-sulfonic acid.

Aromatic diamines suitable for use as tetraazo components or else fordoubling (eg. with cyanuric chloride) and conforming to the formula Veor Vf include for example 1,3-diaminobenzene,1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene,1,4-diaminobenzene-2-sulfonic acid, 1,4-diamino-2-methylbenzene,1,4-diamino-2-methoxybenzene, 1,3-diamino-4-methylbenzene,1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5-methylbenzene,1,6-diaminonaphthalene-4-sulfonic acid,2,6-diaminonaphthalene-4,8-disulfonic acid, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfone,4,4′-diaminostilbene-2,2′-disulfonic acid, 2,2′-diaminodiphenyl sulfone,2,2′-sulfonyldianiline-4,5-disulfonic acid, 4,4′-diaminobenzophenone,4,4′-diamino-3,3′-dinitrobenzophenone,3,3′-diamino-4,4′-dichlorobenzophenone, 4,4′- or 3,3′-diaminobiphenyl,4,4′-diamino-3,3′-dichlorobiphenyl, 4,4′-diamino-3,3′-dimethoxy- or-3,3′-dimethyl- or -2,2′-dimethyl- or -2,2′-dichloro- or-3,3′-diethoxy-biphenyl,4,4′-diamino-3,3′-dimethyl-6,6′-dinitrobiphenyl,4,4′-diaminobiphenyl-2,2′- or -3,3′-disulfonic acid,4,4′-diamino-3,3′-dimethyl- or -3,3′-dimethoxy- or-2,2′-dimethoxy-biphenyl-6,6′-disulfonic acid,4,4′-diamino-2,2′,5,5′-tetrachlorobiphenyl,4,4′-diamino-3,3′-dinitrobiphenyl,4,4′-diamino-2,2′-dichloro-5,5′-dimethoxybiphenyl,4,4′-diaminobiphenyl-2,2′- or -3,3′-dicarboxylic acid,4,4′-diamino-3,3′-dimethylbiphenyl-5,5′-disulfonic acid,4,4′-diamino-2-nitrobiphenyl, 4,4′-diamino-3-ethoxy- or-3-hydroxy-sulfonylbiphenyl,4,4′-diamino-3,3′-dimethylbiphenyl-5-sulfonic acid,4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane,4,4′-diamino-2,2′,3,3′-tetramethyldiphenylmethane,4,4′-diaminodiphenylethane, 4,4′-diaminostilbene or4,4′-diaminodiphenylmethane-3,3′-dicarboxylic acid.

Aromatic radicals D of diazo components of the aniline oraminonaphthalene series which bear further fiber-reactive radicals arederived for example from amines of the formulae VIa-c

where F¹, F², p, q and L⁷ are each as defined above, e and f areidentical or different and each is independently of the other 0 or 1,and V is a fiber-reactive radical.

Fiber-reactive radicals V are derived for example from the radical E orare, as observed above, other additively or substitutively reactingfiber-reactive radicals.

Aromatic amines which form the basis of the derivatives of the formulaVIa, VIb or VIc which have a fiber-reactive radical V include forexample 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid,1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diaminobenzene,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,3-diamino-4-methylbenzene, 1,4-diaminobenzene-2,6-disulfonic acid,1,5-diamino-4-methylbenzene-2-sulfonic acid,1,5-diamino-4-methoxybenzene-2-sulfonic acid,1,6-diaminonaphth-2-ol-4-sulfonic acid,1,6-diaminonaphthalene-4-sulfonic acid,2,6-diaminonaphthalene-4,8-disulfonic acid,2,6-diaminonaphth-1-ol-4,8-disulfonic acid,1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5-methylbenzene,2,6-diaminophenol-4-sulfonic acid,5-aminomethyl-2-aminonaphthalene-1-sulfonic acid,5-(N-methylaminomethyl)-2-aminonaphthalene-1-sulfonic acid,4,4′-diaminostilbene-3,3′-dicarboxylic acid,4-(N-methylaminomethyl)aniline-2-sulfonic acid or3-(N-methylaminomethyl)aniline-6-sulfonic acid.

The radicals K of the coupling component are preferably selected fromthe benzene, naphthalene, pyrazole, pyridine, pyrimidine, indole orN-arylacetoacetamide series and may also bear fiber-reactive groups.

Coupling components free of fiber-reactive groups are preferablycompounds of the naphthalene, aniline, pyrazolone, aminopyrazole,2,6-diaminopyridine, pyridone, hydroxypyrimidine, indole,N-arylacetoacetamide series and correspond for example to the compoundsof the formulae VII a-m

where

m is 0, 1, 2 or 3,

p is 0, 1 or 2,

R¹ is hydrogen or C₁-C₄-alkyl-,- unsubstituted or hydroxyl-, cyano-,carboxyl-, hydroxysulfonyl-, sulfato-, methoxycarbonyl-, ethoxycarbonyl-or acetoxy-substituted,

R² is hydrogen, C₁-C₄-alkyl, unsubstituted or hydroxyl-, cyano-,carboxyl-, hydroxysulfonyl-, sulfato-, methoxycarbonyl-, ethoxycarbonyl-or acetoxy-substituted, benzyl or unsubstituted or C₁-C₄-alkyl-,C₁-C₄-alkoxy-, chlorine- or hydroxysulfonyl-substituted phenyl,

R³ is hydrogen or unsubstituted or hydroxysulfonyl- orcarboxyl-substituted C₁-C₄-alkyl,

R⁴ is C₁-C₆-alkylureido, phenylureido, unsubstituted or chlorine-,methyl-, methoxy-, nitro-, hydroxysulfonyl- or carboxyl-substituted,C₁-C₆-alkanoylamino, unsubstituted or hydroxysulfonyl- orchlorine-substituted, cyclohexylcarbonylamino, benzoylamino,unsubstituted or chlorine-, methyl-, methoxy-, nitro-, hydroxysulfonyl-or carboxyl-substituted, or hydroxyl,

R⁵ is hydrogen, C₁-C₆-alkyl, especially C₁-C₄-alkyl, both unsubstitutedor phenyl-, C₁-C₄-alkoxy-, hydroxyl-, phenoxy- orC₁-C₄-alkanoyloxy-substituted, C₅-C₇-cycloalkyl, hydroxysulfonylphenyl,C₁-C₄-alkanoyl, carbamoyl, mono- or di-(C₁-C₄)-alkylcarbamoyl,phenylcarbamoyl or cyclohexylcarbamoyl,

R⁶ is C₁-C₄-alkoxy, chlorine, bromine, hydroxysulfonyl,C₁-C₄-alkanoylamino, amino, ureido, methylsulfonylamino,ethylsulfonylamino, dimethylaminosulfonylamino, methylamino, ethylamino,dimethylamino or diethylamino,

R⁷ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxysulfonyl, chlorine orbromine,

T is the radical of a benzene or naphthalene ring,

T¹ is C₁-C₄-alkyl, cyclohexyl, benzyl or unsubstituted or fluorine-,chlorine-, bromine-, methoxy-, nitro-, hydroxysulfonyl-, carboxyl-,acetyl-, acetylamino-, methylsulfonyl-, sulfamoyl- orcarbamoyl-monosubstituted, -disubstituted or -trisubstituted phenyl,

R⁸ is methyl, carboxyl, C₁-C₄-alkoxycarbonyl or phenyl,

R⁹ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, acetyl, cyano, carboxyl,hydroxysulfonyl, C₁-C₄-alkoxycarbonyl, hydroxyl, carbamoyl, mono- ordi-C₁-C₄-alkylcarbamoyl, fluorine, chlorine, bromine or trifluoromethyl,

R¹⁰ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, cyano, carboxyl,hydroxysulfonyl, acetylamino, C₁-C₄-alkoxycarbonyl, carbamoyl, mono- ordi-(C₁-C₄)-alkylcarbamoyl, fluorine, chlorine, nitro, sulfamoyl, mono-or di-(C₁-C₄)-alkylsulfamoyl, C₁-C₄-alkylsulfonyl, phenylsulfonyl orphenoxy,

R¹¹ is hydrogen or unsubstituted or C₁-C₄-alkoxy- or cyano-substitutedC₁-C₄-alkyl,

R¹² is hydrogen, methyl, hydroxysulfonylmethyl, hydroxysulfonyl, cyanoor carbamoyl,

R¹³ is hydrogen, C₁-C₄-alkyl, unsubstituted or phenyl-,hydroxysulfonylphenyl-, hydroxyl-, amino-, C₁-C₄-alkoxy-, carboxyl-,hydroxysulfonyl-, acetylamino-, benzoylamino- or cyano-substituted,cyclohexyl, phenyl, unsubstituted or carboxyl-, hydroxysulfonyl-,benzoylamino-, acetylamino-, methyl-,methoxy-, cyano- orchlorine-substituted, or phenyl-, C₁-C₄-alkyl-, C₁-C₄-alkanoyl- orbenzoyl-substituted amino,

R¹⁴ is hydrogen, C₁-C₄-alkyl, phenyl, hydroxyl, cyano, acetyl, benzoyl,carboxyl, methoxycarbonyl, carbamoyl or hydroxysulfonylmethyl and

R¹⁵ is hydrogen, chlorine, bromine, acetylamino, amino, nitro,hydroxysulfonyl, sulfamoyl, methylsulfonyl, phenylsulfonyl, carboxyl,C₁-C₄-alkoxycarbonyl, C₁-C₄-alkanoyl, benzoyl, carbamoyl, cyano orhydroxysulfonylmethyl.

U², U³, F¹, F², R¹, R², R³, R⁵, R⁷, T¹, R⁹, R¹⁰, R¹¹, R¹³ and R¹⁴ andalso the below-described radicals G³, G⁵, G¹² and G¹³ are each forexample methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl ortert-butyl.

U², U³ and R⁵ may each also be pentyl, isopentyl, neopentyl,tert-pentyl, hexyl or 2-methylpentyl.

U², U³, R¹, R², R⁵ and R¹³ are each hydroxy-C₁-C₄-alkyl such ashydroxymethyl, 1-hydroxyeth-1-yl, 2-hydroxyeth-1-yl, 1-hydroxyprop-1-yl,2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxyprop-2-yl,2-hydroxyprop-2-yl, 1-hydroxybut-1-yl, 2-hydroxybut-1-yl,3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl,2-hydroxybut-2-yl, 1-hydroxybut-3-yl, 2-hydroxybut-3-yl,1-hydroxy-2-methylprop-3-yl, 2-hydroxy-2-methylprop-3-yl,3-hydroxy-2-methylprop-3-yl or 2-hydroxymethylprop-2-yl.

U², U³, R¹, R², R¹¹ and R¹³ may each also be for example cyanomethyl,cyanoethyl, cyanopropyl or cyanobutyl.

R¹, R², R³ and R¹³ are each for example carboxymethyl, carboxyethyl, 2-or 3-carboxypropyl or 2- or 4-carboxybutyl.

U², U³, R¹, R² and R³ may each also be for examplehydroxysulfonylmethyl, 2-hydroxysulfonylethyl, 2- or3-hydroxysulfonylpropyl, 2- or 4-hydroxysulfonylbutyl.

R¹ and R² may each also be for example 2-sulfatoethyl, 2- or3-sulfatopropyl, 2- or 4-sulfatobutyl, methoxycarbonylmethyl,2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or4-methoxycarbonylbutyl, ethoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-or 3-ethoxycarbonylpropyl, 2- or 4-ethoxycarbonylbutyl, acetoxymethyl,2-acetoxyethyl, 2- or 3-acetoxypropyl, 2- or 4-acetoxybutyl.

R² may also be for example 2-, 3- or 4-methylphenyl, 2-, 3- or4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl,2-, 3- or 4-butylphenyl, 2-, 3- or 4-isobutylphenyl, 2-, 3- or4-sec-butylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-propoxyphenyl,2-, 3- or 4-isopropoxyphenyl, 2-, 3- or 4-butoxyphenyl, 2-, 3- or4-isobutoxyphenyl, 2-, 3- or 4-sec-butoxyphenyl, 2-, 3- or4-tert-butoxyphenyl, 2-, 3- or 4-chlorophenyl.

R², R⁵ and T¹ may each also be for example 2-, 3- or4-hydroxysulfonylphenyl.

R⁴ is for example methylureido, ethylureido, propylureido, butylureido,pentylureido, hexylureido, formylamino, acetylamino, propionylamino,butyrylamino, isopropylcarbonylamino, valerylamino,isobutylcarbonylamino, sec-butylcarbonylamino, tert-butylcarbonylamino,pentylcarbonylamino.

R⁵ and R¹³ are each for example benzyl, 1-phenylethyl, 2-phenylethyl,1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl,1-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl,1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 3-phenylbut-2-yl,4-phenylbut-2-yl, 1-(phenylmethyl)-eth-1-yl,1-(phenylmethyl)-1-(methyl)-eth-1-yl or 1-(phenylmethyl)-prop-1-yl,preferably benzyl or 2-phenylethyl.

R⁵, R¹¹ and R¹³ may each also be for example methoxymethyl,ethoxymethyl, n-propoxymethyl, (1-methylethoxy)methyl, n-butoxymethyl,(1-methylpropoxy)methyl, (2-methylpropoxy)methyl,(1,1-dimethylethoxy)methyl, 2-(methoxy)ethyl, 2-(ethoxy)ethyl,2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl,2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl,2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl,2-(n-propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(n-butoxy)propyl,2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl,2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)propyl,3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl,3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl,3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl,2-(n-propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl,2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl,2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl,3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(n-butoxy)butyl,3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl,3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl,4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl,4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or4-(1,1-dimethylethoxy)butyl.

R⁵ can also be for example phenoxymethyl, 2-phenoxyethyl, 2- or3-phenoxypropyl, 2- or 4-phenoxybutyl, formyloxymethyl,2-(formyloxy)ethyl, 3-(formyloxy)propyl, 2- or 4-(formyloxy)butyl,methylcarbonyloxymethyl, 2-(methylcarbonyloxy)ethyl, 2- or3-(methylcarbonyloxy)propyl, 2- or 4-(methylcarbonyloxy)butyl,ethylcarbonyloxymethyl, 2-(ethylcarbonyloxy)ethyl, 2- or3-(ethylcarbonyloxy)propyl, 2- or 4-(ethylcarbonyloxy)butyl,propylcarbonyloxymethyl, 2-(propylcarbonyloxy)ethyl, 2- or3-(propylcarbonyloxy)propyl, 2- or 4-(propylcarbonyloxy)butyl,cyclopentyl, cyclohexyl, cycloheptyl.

R⁵, R¹⁵ and also the below-described radicals G⁴ are each for exampleformyl, acetyl, propionyl, butyryl, isobutyryl.

F¹, F², R⁵, R⁹, R¹⁰ and also the below-described radicals G⁴ are eachfor example mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono-or dipropylcarbamoyl, mono- or dibutylcarbamoyl.

F¹, F², R⁶, R⁷, R⁹, R¹⁰ and also the below-described radicals G³ and G⁵can each also be for example methoxy, ethoxy, propoxy, isopropoxy,butoxy, sec-butoxy, isobutoxy, tert-butoxy.

R⁶ and R¹³ are each for example formylamino, methylcarbonylamino,ethylcarbonylamino, propylcarbonylamino, isopropylcarbonylamino.

T¹ may also be for example 2-, 3- or 4-fluorophenyl, 2-, 3- or4-chlorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-methoxyphenyl, 2-,3- or 4-nitrophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or4-acetylphenyl, 2-, 3- or 4-acetylaminophenyl, 2-, 3- or4-methylsulfonylphenyl, 2-, 3- or 4-sulfamoylphenyl or 2-, 3- or4-carbamoylphenyl.

F¹, F², R⁸, R⁹, R¹⁰, R¹⁵ and also the below-described radicals R¹⁶ mayalso be for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl,sec-butoxycarbonyl or tert-butoxycarbonyl.

F² and R¹⁰ may also be for example mono- or dimethylsulfamoyl, mono- ordiethylsulfamoyl, mono- or dipropylsulfamoyl, mono- or dibutylsulfamoyl,methylsulfonyl, ethylsulfonyl, propylsulfonyl or butylsulfonyl.

R¹³ may also be for example hydroxysulfonylphenylmethyl,2-hydroxysulfonylphenylethyl, 2- or 3-hydroxysulfonylphenylpropyl, 2- or4-hydroxysulfonylphenylbutyl, aminomethyl, 2-aminoethyl, 2- or3-aminopropyl, 2- or 4-aminobutyl, hydroxysulfonylmethyl,2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, 2- or4-hydroxysulfonylbutyl, acetylaminomethyl, 2-acetylaminoethyl, 2- or3-acetylaminopropyl, 2- or 4-acetylaminobutyl, benzoylaminomethyl,2-benzoylaminoethyl, 2- or 3-benzoylaminopropyl, 2- or4-benzoylaminobutyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or4-hydroxysulfonylphenyl, 2-, 3- or 4-benzoylaminophenyl, 2-, 3- or4-acetylaminophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or4-methoxyphenyl, 2-, 3- or 4-cyanophenyl, 2-, 3- or 4-chlorophenyl,phenylamino, methylamino, ethylamino, propylamino, isopropylamino,butylamino, isobutylamino, sec-butylamino, tert-butylamino orbenzoylamino.

The radicals L⁵ and also the below-described radicals L⁸ are each forexample (CH₂)₂, (CH₂)₃, (CH₂)₄, CH(CH₃)CH₂, CH(CH₃)CH(CH₃), (CH₂)₅ or(CH₂)₆.

L⁵ may also be for example (CH₂)₂O(CH₂)₂, (CH₂)₃O(CH₂)₂,(CH₂)₂O(CH₂)₂O(CH₂)₂, (CH₂)₂S(CH₂)₂, (CH₂)₃S(CH₂)₂,(CH₂)₂S(CH₂)₂S(CH₂)₂, (CH₂)₂NH(CH₂)₂, (CH₂)₃NH(CH₂)₂,(CH₂)₂NH(CH₂)₂NH(CH₂)₂,

L⁶ and L¹¹ are each CH₂, (CH₂)₂, (CH₂)₃, (CH₂)₄, CH(CH₃)CH₂orCH(CH₃)CH(CH₃).

In what follows, coupling components KH are recited by way of example.Specific examples of naptholsulfonic acids are 1-naphthol-3-sulfonicacid, 1-naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid,1-naphthol-8-sulfonic acid, 1-naphthol-3,6-disulfonic acid,1-naphthol-3,8-disulfonic acid, 2-naphthol-5-sulfonic acid,2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid,2-naphthol-8-sulfonic acid, 2-naphthol-3,6-disulfonic acid,2-naphthol-6,8-disulfonic acid, 2-naphthol-3,6,8-trisulfonic acid,1,8-dihydroxynaphthalene-3,6-disulfonic acid,2,6-dihydroxynapthalene-8-sulfonic acid and2,8-dihydroxynaphthalene-6-sulfonic acid.

Further examples are 1-naphthylamine, N-phenyl-1-naphthylamine,N-ethyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1-naphthol,2-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.

Examples of aminonaphthalenesulfonic acids are1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid,1-naphthylamine-8-sulfonic acid, 2-naphthylamine-3,6-disulfonic acid,2-naphthylamine-5,7-disulfonic acid, 2-naphthylamine-6,8-disulfonicacid, 2-hydroxysulfonylmethylaminonaphthalene-5-sulfonic acid and2-hydroxysulfonylmethylaminonaphthalene-6-sulfonic acid.

Examples of aminonaphtholsulfonic acids are1-amino-5-hydroxynaphthalene-7-sulfonic acid,1-amino-8-hydroxynaphthalene-4-sulfonic acid,1-amino-8-hydroxynaphthalene-2,4-disulfonic acid,1-amino-8-hydroxynaphthalene-3,6-disulfonic acid,1-amino-8-hydroxynaphthalene-4,6-disulfonic acid,2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-amino-8-hydroxynaphthalene-6-sulfonic acid,2-amino-8-hydroxynaphthalene-3,6-disulfonic acid,2-amino-5-hydroxynaphthalene-1,7-disulfonic acid,3-amino-7-hydroxysulfonylmethyl-8-hydroxynaphthalene-3,6-disulfonicacid, 2-amino-7-hydroxysulfonylmethyl-8-hydroxynaphthalene-6-sulfonicacid, 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid,1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid,1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid,2-methylamino-8-hydroxynaphthalene-6-sulfonic acid,2-hydroxysulfonylmethylamino-8-hydroxynaphthalene-6-sulfonic acid,2-hydroxysulfonylmethylamino-7-hydroxysulfonylmethyl-8-hydroxynaphthalene-6-sulfonicacid, 2-hydroxysulfonylmethylamino-8-hydroxynaphthalene-3,6-disulfonicacid,2-hydroxysulfonylmethylamino-7-hydroxysulfonylmethyl-8-hydroxynaphthalene-3,6-disulfonicacid, 2-(3′- or4′-hydroxysulfonylphenylamino)-8-hydroxynaphthalene-6-sulfonic acid,2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid and2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid.

Examples of benzene coupling components are o- or m-toluidine, o- orm-anisidine, cresidine, 2,5-dimethylaniline, 2,5-dimethoxyaniline,m-aminoacetanilide, 3-amino-4-methoxyacetanilide,3amino-4-methylacetanilide, m-aminophenylurea, N-methylaniline,N-methyl-m-toluidine, N-ethylaniline, N-ethyl-m-toluidine,N-(2-hydroxyethyl)aniline and N-(2-hydroxyethyl)-m-toluidine.

Examples of pyrazolone coupling components are 3-methyl-, 3-carboxy- or3-(C₁-C₄-alkoxycarbonyl)-pyrazol-5-ones with or without substitution inposition 1 by unsubstituted or methyl-, ethyl-, fluorine-, chlorine-,bromine-, trifluoromethyl-, methoxy-, ethoxy-, cyano-, phenoxy-,phenylsulfonyl-, methylsulfonyl-, hydroxysulfonyl-, acetylamino-,nitro-, hydroxyl-, carboxyl-, carbamoyl- or sulfamoyl-substituted phenylor by hydroxysulfonyl-substituted 1- or 2-naphthyl. Examples are1-phenyl-, 1-(2′-chlorophenyl)-, 1-(2′-methoxyphenyl)-,1-(2′-methylphenyl)-, 1-(1′,5′-dichlorophenyl)-,1-(2′,6′-dichlorophenyl)-, 1-(2′-methyl-6′-chlorophenyl)-,1-(2′-methoxy-5′-methylphenyl)-,1-(2′-methoxy-5′-hydroxysulfonylphenyl)-,1-(2′,5′-dichloro-4′-hydroxysulfonylphenyl)-,1-(2′,5′-dihydroxysulfonylphenyl)-, 1-(2′-carboxyphenyl)-,1-(3′-hydroxysulfonylphenyl)-, 1-(4′-hydroxysulfonylphenyl)- or1-(3′-sulfamoylphenyl)-3-carboxypyrazol-5-one, 1-(3′- or4′-hydroxysulfonylphenyl)-, 1-(2′-chloro 4′- or-5′-hydroxysulfonylphenyl)-, 1-(2′-methyl-4′-hydroxysulfonylphenyl)-,1-(2′,5′-dichlorophenyl)-, 1-(4′,8′-dihydroxysulfonyl-1-naphthyl)-,1-(6′-hydroxysulfonyl-1-naphthyl)-3-methylpyrazol-5-one, ethyl1-phenylpyrazol-5-one-3-carboxylate, ethyl pyrazol-5-one-3-carboxylateor pyrazol-5-one-3-carboxylic acid.

Other pyrazole coupling components include for example 1-methyl-,1-ethyl-, 1-propyl-, 1-butyl-, 1-cyclohexyl-, 1-benzyl- or1-phenyl-5-aminopyrazole, 1-(4′-chlorophenyl)-,1-(4′-methylphenyl)-5-aminopyrazole or1-phenyl-3-methyl-5-aminopyrazole.

N-Arylacetoacetamides are particularly acetoacetanilide or itsderivatives having one or more substituents selected from the groupconsisting of chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino,hydroxysulfonyl, carboxyl, carbamoyl and sulfamoyl in the phenyl ring.

Pyridine coupling components are the derivatives described in DE-A-2 260827, for example.

Suitable pyrimidine coupling components include for example thecompounds recited in DE-A-2 202 820, DE-A-2 308 663 or DE-A-3 119 349.Also suitable are barbituric acid and its N-substitution products.Suitable N-substituents include in particular C₁-C₄-alkyl or phenyl.

Examples of suitable indole coupling components are 2-methylindole,2-phenylindole, 2-phenylindole-5-sulfonic acid, 1-methyl-2-phenylindole,1-(2′-hydroxyethyl)-, 1-(2′-carboxyethyl)-,1-(2′-carbamoylethyl)-2-methylindole or -2-phenylindole.

Examples of suitable pyridone coupling components are1-ethyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one,1-(2′-hydroxyethyl)-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one,1-phenyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonylmethylpyrid-6-one,1-methyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one,1-methyl-2-hydroxy-5-acetylpyrid-6-one,1,4-dimethyl-2-hydroxy-5-cyanopyrid-6-one,1,4-dimethyl-5-carbamoylpyrid-6-one,2,6-dihydroxy-4-ethyl-5-cyanopyridine,2-hydroxy-4-ethyl-5-carbamoylpyrid-6-one,1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonylmethylpyrid-6-one,1-methyl-2-hydroxy-4-methyl-5-methylsulfonylpyrid-6-one and1-carboxymethyl-2-hydroxy-4-ethyl-5-phenylsulfonylpyrid-6-one.

Coupling components KH of the naphthalene, benzene, pyrazolone,aminopyrazole, 2,6-diaminopyridine, pyridone, hydroxypyrimidine,aminopyrimidine, indole or N-arylacetoacetamide series which contain afiber-reactive group include for example compounds of the formulaeVIIIa-k

where

T² is the radical of a benzene or naphthalene ring,

R¹⁶ is methyl, carboxyl, C₁-C₄-alkoxycarbonyl or phenyl,

L⁸ is C₁-C₆-alkylene, and

R¹, R², R⁵, R⁶, R⁹, R¹⁰, R¹¹, R¹², R¹⁴, R¹⁵, p and V are each as definedabove.

Pyrazolone coupling components bearing fiber-reactive radicals V arederived for example from the following pyrazolones: 1-(3′- or4′-aminophenyl)-, 1-(2′-hydroxysulfonyl-5′-aminophenyl)- or1-(2′-methoxy-5′-aminophenyl)-3-carboxypyrazol-5-one, 1-(3′- or4′-aminophenyl)- or1-(6′-amino-4′,8′-dihydroxysulfonylnaphth-2′-yl)-3-carboxypyrazol-5-one.

Particular preference for use in hair dyeing is given to dyes of theformula IX

E—N═N—K¹  (IX),

where E is as defined above and K¹ is the radical of a couplingcomponent of the benzene, naphthalene, pyrazole or pyridine series whichoptionally has further fiber-reactive groups, especially the group E,the group of the formula SO₂—Y, where Y is as defined above, or those ofthe halotriazine series.

Particular preference is given to the use of reactive dyes havingamino-substituted naphthalenes as coupling components, of which the2-aminonaphthalenesulfonic acids which are coupled in the 1-positionespecially are notable. The dyes of the general formula X

where

G¹ is hydrogen or hydroxysulfonyl,

G² is hydrogen or hydroxyl, and

E, R² and R³ are each as defined above, are therefore preferred aboveall.

Of the group of the reactive dyes of the formula X, emphasis is given tothose in which R² and/or R³ are each hydrogen, C₁-C₄-alkyl which aresubstituted by hydroxysulfonyl or carboxyl, especially hydrogen,hydroxysulfonylmethyl or carboxymethyl.

Of the group of the dyes of the formula X, preference is given to thosein which R² and/or R³ are each hydrogen, hydroxysulfonylmethyl orcarboxymethyl, G¹ is hydrogen or hydroxysulfonyl, G² is hydrogen orhydroxyl and, in the radical E, L³ is a direct bond and A¹ ishydroxysulfonyl.

Particular preference is further given to the use of dyes of theformulae XIa and XIb

where the radical E is as defined above and D is the radical of a diazocomponent of the aniline or naphthalene series which optionally hasfurther fiber-reactive groups, especially the group E, the group SO₂Y orthose of the halotriazine series.

Preference for use is further given to the reactive dyes of the formulaXII

where

E and K¹ are each as defined above,

L⁹ is a radical of the formula O₂S—NZ¹, OC—NZ¹, Z¹N—SO₂, Z¹N—CO,Z¹N—CO—NZ², NZ¹ or

where Z¹, Z² and Hal are each as defined above, and

G³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, chlorine or hydroxysulfonyl.

Preference for hair dyeing is further given to reactive dyes of theformula XIII

where

D¹, E and L⁹ are each as defined above,

G⁴ is C₁-C₄-alkanoyl, carbamoyl, mono- or di(C₁-C₄)alkylcarbamoyl,phenylcarbamoyl or cyclohexylcarbamoyl, and

G⁵ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxysulfonyl or chlorine.

Preference is further given to using reactive dyes of the formulae XIVaand XIVb

where D, E and L⁹ are each as defined above and the hydroxysulfonylgroup is disposed in ring position 5 or 6.

Preference for use in hair dyeing is further given to reactive dyes ofthe formula XV

where D, E and L⁹ are each as defined above and the group —L⁹—E isdisposed in ring position 6 or 7.

Useful compounds further include those of the formula XVI

where D¹, E and L⁹ are each as defined above and p and r areindependently of each other 0, 1 or 2.

Useful compounds further include those of the formula XVII

where one of the two radicals G⁶ and G⁷ is D, D having theabovementioned meaning, and the other is the radical

or else G⁶ and G⁷ are each a radical of the formula

where L⁹ and E are each as defined above.

Instead of the azo dye radicals, the dyes of the formula I may alsocontain corresponding metal complex azo dye radicals. Contemplatedcomplexing metals include in particular copper, cobalt, chromium, nickelor iron, of which copper, cobalt or chromium are preferred.

The metallized groups are preferably disposed in each case ortho to theazo group, for example in the form of o,o′-dihydroxy-,o-hydroxy-o′-carboxy-, o-carboxy-o′-amino- or o-hydroxy-o′-amino-azogroups.

W in the formula I may also be for example the radical of a metallizedformazan dye, in which case copper formazans should be mentioned inparticular. Copper formazans are known per se and described for examplein K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. III, AcademicPress, New York, London, 1970.

Particular preference is given to copper formazan dyes of the formulaXIII

where

Cat^(⊕) is the equivalent of a cation,

G⁸ ₁, G⁹ and G¹⁰ are identical or different and each is independently ofthe other hydrogen or hydroxysulfonyl,

v is 0 or 1,

w is 0 or 1, and

E and L⁹ are each as defined above, with the proviso that v and w arenot both 0.

Kat^(⊕) in the formula XVIII is the equivalent of a cation. It is eithera proton or derived from metal or ammonium ions. Metal ions are inparticular the lithium, sodium or potassium ions. Ammonium ions for thepurposes of this invention are the abovementioned substituted orunsubstituted ammonium cations.

Preferred cations are protons or lithium, sodium or potassium ions, themetal cations mentioned also being preferred cations when the reactivedyes XVIII are present in salt form.

One method of preparing the formazans underlying these dyes is describedin EP-A-315 046 for example.

W in the formula I may also be for example the radical of ananthraquinone dye. Anthraquinones are known per se and described forexample in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. II,Academic Press, New York, 1952.

Particular preference for dyeing hair is given to anthraquinone dyes ofthe formula XIX

where

E and L⁹ are each as defined above,

x is 0 or 1

F³ and F⁴ are independently of each other hydrogen or methyl

and one of the two radicals F⁵ and F⁶ is hydrogen or methyl and theother is hydroxysulfonyl.

W in the formula I may also be for example the radical of atriphendioxazine dye. Triphendioxazines are known per se and describedfor example in EP-A-141 359 or EP-A-311 969.

Suitable examples include triphendioxazine dyes of the formula XX

where

E and L⁹ are each as defined above,

G¹¹ is hydroxysulfonyl or the radical SO₂—C₂H₄—SO₃H,

L¹⁰ is C₂-C₄-alkylene or phenylene, and

L¹¹ is oxygen, imino or C₁-C₄-alkylimino.

W in the formula I may also be for example the radical of a metallizedphthalocyanine dye. Phthalocyanines are known per se and described forexample in F. H. Moser, D. L. Thomas, The Phthalocyanines, Vol. II, CRCPress, Boca Raton, Fla. 1983.

Particular preference is given to the phthalocyanine dyes of the formulaXXI

where

Pc is the phthalocyanine radical,

G¹² and G¹³ are independently of each other hydrogen or C₁-C₄-alkyl,

L¹² is imino or C₁-C₄-alkylimino,

L¹³ is a direct bond or C₁-C₄-alkylene,

Me is copper or nickel,

g is 0, 1 or 2,

h is 0, 1 or 2,

i is 1 or 2,

j is 0, 1, 2 or 3

and E, L⁹ and L¹⁰ are each as defined above.

Preference is further given to reactive dyes of the formula XXII

where

G¹⁴ is methyl or carboxyl,

G¹⁵ is hydrogen or hydroxysulfonyl,

and E is as defined above.

Preference is likewise given to reactive dyes of the formula XXIII

where

G¹⁶ is hydrogen or methyl,

G¹⁷ is hydrogen, cyano, carbamoyl or hydroxysulfonylmethyl,

G¹⁸ is methyl or ethyl,

and E is as defined above.

Since hair dyeing is generally not carried out with pure dyes, the useof mixtures of dyes of the formula I is expressly encompassed.

Furthermore, the reactive dyes of the formula I may be admixed withdirect dyes such as azo dyes, anthraquinone dyes or nitro dyes of thebenzene series to weaken or strengthen the colors produced.

The reactive dyes of the formula I can be prepared in a conventionalmanner.

When the radical W is linked to the fiber-reactive group E via a diazobridge, the dyes of the invention are obtained by, for example,diazotizing and coupling the fiber-reactive compound of the formulaXXIVa

H₂N—E  (XXIVa),

where E is as defined above, in a conventional manner with a couplingcomponent of the formula XXV

W¹—H  (XXV)

where W¹ is the radical of a coupling component, of a monoazo dye oradditionally, when b=0, of a disazo dye, which may each have furtherreactive groups.

If, on the other hand, the radical W is linked to the fiber-reactivegroup E via one of the bridge members L⁹ recited in case 2, the dyes ofthe invention can be prepared by reacting a suitable dye of the formulaXXVI

W²—G¹⁹  (XXVI),

where W² is the radical of a chromophore which optionally has furtherreactive groups and is derived from an optionally metallized mono- ordisazo dye, a triphendioxazine, an anthraquinone, a metallized formazanor a metallized phthalocyanine and G¹⁴ is an amino radical of theformula NHZ¹ or an acid halide radical of the formula COHal or SO₂Hal,where Z¹ and Hal are each as defined above, with a fiber-reactivecompound of the formula XXVIb

G²⁰—E  (XXVIb),

where E is as defined above and G²⁰ is one of the radicals G¹⁹, with theproviso that, in either case, an amine reacts with an acid halide.

When L⁹ (case 2) is a urea bridge or a triazine radical, the synthesissteps customary with these classes of compounds are included as well.

It is also possible to start from such precursors of compounds of theformula XXVI as form part of the later chromophore and to react themfirst with the fiber-reactive compound XXVIb and then to construct thechromophore radical W².

When b in the formula I is 1, the bridged chromophores can be obtainedfor example by either bridging the finished individual chromophores orelse by first bridging suitable intermediates and then constructing therespective chromophoric systems.

Furthermore, U.S. Pat. No. 4,066,638, EP-A-107 614, EP-A-107617,EP-A-559 617, EP-A-581 729, EP-A-693 536, DE-A-3441272, DE-A-3441273,DE-A-4437265, EP-A-637615, EP-A-318968, JP-A-7118830, JP-A-7128904,NL-A-7410432, EP-A-637615, DE-A-19600765, DE-A-4434989, DE-A-19523245DE-A-2 154 942 and prior German publication DE-A 19611667, for example,describe dyes which fall within the general formula I.

The use in hair dyeing of the dyes recited as examples in thesedocuments is expressly encompassed.

The present invention further provides cosmetic preparations comprisingthe above dyes as well as customary hair dyeing assistants.

The dyes are used in dissolved form in an aqueous cosmeticallyacceptable medium. In the aqueous cosmetically acceptable carrier, thepH varies within the range from 5 to 9 and is preferably 6-8. It isadjusted to the desired value with the aid of mild inorganic or organicbases, salts, weak acids or buffers. Examples are ammonia, ammoniumcarbonate, potassium carbonate, sodium carbonate, sodium hydroxide suchas mono-, di- or triethanolamine, disodium hydrogenphosphate, sodiumcitrate or sodium borate.

The dyes are present in the hair colorants in proportions from 0.01 to10% by weight, based on the total weight of the preparation.

Customary assistants in cosmetic preparations for hair dyeing areanionic, cationic, nonionic or amphoteric surfactants or mixturesthereof. Suitable surfactants are soaps, alkylbenzenesulfonates,alkylnaphthalenesulfonates, sulfates, ether sulfates and sulfonates offatty alcohols, quaternary ammonium salts, such astrimethylcetylammonium bromide, cetylpyridinium bromide, quaternium 1 toX (INCI), cocoyltrimethylammonium methylsulfate (INCI),hydroxyethylcetyldimomium phosphate (INCI), cetyltrimethylammoniumchloride, optionally ethoxylated fatty acid ethanolamides,polyethoxylated acids, alcohols or amines, polyglycerated alcohols,polyethoxylated or polyglycerated alkylphenols and also polyethoxylatedalkyl sulfates. Surfactants are present in the compositions of theinvention in an amount from 0.5 to 40% by weight, based on the totalweight of the preparation.

Further customary assistants are organic solvents such as solubilizers,eg. C₁-C₄-alcohol such as ethanol and isopropanol, glycols, glycolethers such as ethylene glycol, propylene glycol, 2-methoxyethanol,2-ethoxyethanol or 2-butoxyethanol, and also glycerol. Solvents aregenerally present in an amount of 0-40% by weight, based on the totalweight of the preparation.

To simplify the handling of the preparation, it is customary to addthickeners to the preparations of the invention as assistants. Customarythickeners are cellulose derivatives such as methyl-, hydroxymethyl-,hydroxyethyl-, hydroxypropyl- or carboxymethyl-cellulose, sodiumalginate, gum arabic, xanthan gum, tragacanth, acrylic acid polymers,polyvinylpyrrolidone, vinyl acetate/crotonic acid copolymers, vinylacetate/vinylpyrrolidone copolymers, butyl vinyl ether/maleic anhydridecopolymers, methyl vinyl ether/maleic anhydride copolymers, or aninorganic thickener such as bentonite. These thickeners are generallyused in an amount of up to 5% by weight based on the total weight of thepreparation.

Hair-cosmetic preparations which are to be used in the form of gelsfurther comprise gel-forming substances such as, for example, carbomers(INCI). For certain caring properties, the preparations may furthercomprise cationic poymers and silicone compounds. Suitable cationicpolymers are, for example, polyquaternium 1 to x as per INCI, copolymersof vinylpyrrolidone/vinylimidazolium salts (Luviquat® FC, Luviquat HM,manufacturer: BASF), copolymers of vinylpyrrolidone/dimethylaminoethylmethacrylate, quaternized with diethyl sulfate (Luviquat PQ 11);cationic cellulose derivatives (Polyquaternium-4 and 10), acrylamidocopolymers (Polyquaternium-7) and cationic guar gum derivatives, eg.guar hydroxypropyltriminium chloride (INCI). Suitable silicone compoundsare, for example, polyalkylsiloxanes, polyarylsiloxanes,polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.

Further customary assistants are mild antioxidants which do not reactwith the dyes, penetrants, sequestrants, buffers, perfume oil,sunscreens (UV-A and UV-B), preservatives, hair-cleaning products andbiologically active substances such as pantheonol, bisabolol andvitamins, for example of type A, C and E.

The cosmetic preparations of the invention can be used for dyeing hairin liquid form, generally thickened, as cream, paste, as gel or in someother suitable form.

In a preferred application, the preparation is applied to the hair,allowed to act on the hair for from 5 to 50 minutes, preferably from 10to 30 minutes, and then the hair is rinsed and, if necessary, washedwith a conventional shampoo.

A warm preparation or external heat can be used to speed up the dyeingor deepen the dyeing over the same treatment time. Preference is givento using temperatures within the range from 20 to 40° C.

The reactive dyes of the formula I produce uniform dyeings and goodcoverage of white hair. The dyeings are lightfast, washfast, weatherfastand rubfast.

Furthermore, reactive dyes and their alternative dyeing method make itpossible to dispense with H₂O₂ as an oxidant in the dyeing process. Whatis particularly advantageous here is the fact that the hue ispredetermined by the dye and not developed on the hair. This simplifiesthe preparation of dye mixtures and shading.

They are furthermore known to be physiologically safe from their use astextile dyes.

The Examples which follow illustrate the invention.

EXAMPLE 1

1.25 g of the reactive dye of the formula 1

were dissolved in 25 ml of water and the solution was adjusted to pH 7with sodium hydrogenphosphate. After the solution was heated to 36° C.,a bleached strand of human hair (2 g) was immersed into the solution for20 minutes. Thereafter the hair was rinsed with water and air dried. Adeep reddish scarlet hair dyeing (λ max=508 nm, reflectance) wasobtained.

Dyeings were obtained under similar conditions with the dyes recited inthe examples which follow, where E¹ and E² are the radicals of theformulae

respectively.

EXAMPLE 2

NH₂ (described in Ex. 4 of U.S. Pat. No. 4,066,638) bluish red (λmax=534, reflectance)

EXAMPLE 3

(described in Ex. 1 of DE-A 214942) bluish red (λ max=539, reflectance)

EXAMPLE 4

(described in Ex. 1 of DE-A-19523245) dark blue

EXAMPLE 5

(prepared similarly to Ex. 1 of DE-A-19523245) dark blue

EXAMPLE 6

(prepared similarly to Ex. 1 of DE-A-19523245) dark blue

EXAMPLE 7

(similarly to Ex. 79 of U.S. Pat. No. 4,066,638) yellowish brown

Preparation method relating to Example 1

131 g of 1-amino-3-(β-sulfatoethylsulfonyl)benzene-4,6-disulfonic acidwere suspended in 700 ml of ice-water and 60 ml of hydrochloric acid(30% strength by weight) and admixed at 0-5° C. with 60 ml of 23%strength by weight sodium nitrite solution added a little at a time.After diazotization had ended, the small excess of nitrite was destroyedwith some amidosulfuric acid. 60 g of 2-aminonaphthalene-5-sulfonic acidin 800 ml of ice-water were added to this reaction mixture at 0-5° C., apH of 2-3 was maintained with sodium acetate, and the batch wasgradually warmed to 20° C. Once diazo compound was no longer detectable,the pH was adjusted to 5 with sodium bicarbonate, and the batch wasclarified by filtration. The dye was precipitated by addition of 500 gof sodium chloride, filtered off with suction and dried at 40° C. underreduced pressure, leaving a readily water-soluble reddish powder. Asimilar dye is described in Example 3 of U.S. Pat. No. 406,638.

The dyes in Examples 2, 3 and 7 were prepared in a similar manner.

Formulation Examples

A) Hair-dyeing Cream

Phase I

1.5 g of ceteareth-6 (and) stearyl alcohol (INCI)

1.5 g of ceteareth-25

6.0 g of cetearyl octanoate

3.0 g of cetearyl alcohol

Phase II

2 g of reactive dye of the formula 1

2 g of propylene glycol

84 g of dist. water

q.s. citric acid/triethanolamine to adjust to pH 7

q.s. preservative

Phase III

q.s. perfume oil

The ingredients were dissolved at 60° C., and then Phase I was added toPhase II. Phase III was added after cooling to 30° C.

A bleached strand of human hair (2 g) was treated with 0.5 g of thedyeing cream and left for 20 min. It was then rinsed with water, leavinga hair dyeing as described in Example 1.

B) Hair-dyeing Lotion

5 g of reactive dye of the formula 1

1.2 g of Natrosol 250 HR (manufacturer: Aqualon), (hydroxyethylcelluloseto INCI)

1 g of propylene glycol

ad 100 g of dist. water

q.s. preservative

A bleached strand of human hair (2 g) was treated with 0.5 g of thedyeing lotion and left for 20 min. It was then rinsed with water,leaving a hair dyeing as described in Example 1.

C) Hair-dyeing Mousse

2 g of reactive dye of the formula 1

3 g of Luviskol® VA 64 (manufacturer: BASF), (PVP/VA copolymer to INCI)

0.45 g of ceteareth-25 (INCI)

0.10 g of dimethicone (INCI)

10 g of propane/butane

ad 100 g of dist. water

q.s. preservative

A bleached strand of human hair (2 g) was treated with 0.5 g of thehair-dyeing mousse, left for 15 min and then rinsed with water. As wellas being deeply colored, the hair was very easy to comb through andlooked cared-for. The hair dyeing obtained was as described in Example1.

D) Hair-dyeing Shampoo

5 g of reactive dye of the formula 1

40 g of sodium laurylethersulfate to INCI (Texapon® N 28, manufacturer:Henkel)

10 g of Tego® Betain L 7 (manufacturer: Goldschmidt) (cocamidopropylbetaine to INCI)

2 g of Gluatin WQ (wheat germ protein)

ad 100 g of dist. water

q.s. preservative

q.s. sodium chloride as thickener

The use of a hair-dyeing shampoo makes it possible to combine cleaningand dyeing of the hair. A bleached strand of human hair (2 g) wastreated with 0.5 g of the hair-dyeing shampoo and rinsed out after 1 minto the disappearance of foam. The hair dyeing obtained was as describedin Example 1.

E) Dyeing Paste

2 g of reactive dye of formula 1

7 g of titanium dioxide

15 g of aerosil® (manufacturer: Degussa)

10 g of Lutrol® F 127 (polyethylene glycol, manufacturer: BASF)

ad 100 g of dist. water

q.s. preservative

A bleached strand of human hair (2 g) was treated with 0.5 g of thehair-dyeing paste, left for 15 min and then rinsed with water. The hairdyeing obtained was as described in Example 1.

F) Hair-dyeing Shampoo

10 g of reactive dye of formula 1

2.20 g of xanthan gum (Keltrol® T, manufacturer: Kelco)

20.0 g of sodium laurylethersulfate

2.50 g of olein diethanolamide

0.10 g of Trilon® B (manufacturer: BASF)

ad 100 g of dist. water

45 q.s. preservative

25 g of the dyeing paste were suspended with 25 ml of dist. water, ableached strand of human hair (2 g) was treated with this dyeing shampooand left for 20 min. It was then rinsed out with water. The hair dyeingobtained was as described in Example 1.

What is claimed is:
 1. A method of dyeing human hair, comprisingapplying to the hair a reactive dye of the formula I:

wherein a is 1 or 2, b is 0 or 1, Y is vinyl or a radical of the formulaC₂H₄Q, where Q is an alkali-detachable group, L³ is a direct bond or abridge member of the formula CO—NH—M¹, where M¹ is C₂-C₆-alkylene withor without interruption by 1 or 2 unadjacent oxygen atoms, imino orC₁-C₄-alkylimino groups, A¹ is hydroxysulfonyl or a radical of theformula SO₂Y, A² is hydrogen, hydroxysulfonyl, methoxy, chlorine,bromine or carboxyl, W is either in case 1) the radical of a couplingcomponent, of a monoazo dye or additionally, when b=0, of a disazo dye,which may each bear further fiber-reactive groups, or in case 2) theradical of a chromophore which optionally has further fiber-reactivegroups and is derived from an optionally metallized mono- or disazo dye,from a triphendioxazine, from an anthraquinone, from a metallizedformazan or from a metallized phthalocyanine, L¹ is either in case 1) anazo bridge or in case 2) a bridge member of the formula O₂S—NZ¹, OC—NZ¹,Z¹N—SO₂, Z¹N—CO, Z¹N—CO—NZ², NZ¹ or

where M² is a direct bond or methylene, Z¹ and Z² are each independentlyof the other hydrogen, C₁-C₆-alkyl or phenyl and X is fluorine, chlorineor bromine, amino, C₁-C₆-alkylamino with or without interruption by 1 or2 unadjacent oxygen atoms, imino or C₁-C₄-alkylimino groups and with orwithout hydroxyl substitution, N-pyrrolidinyl, N-piperidinyl,N-morpholinyl, N-piperazinyl or N-(C₁-C₄)-alkylpiperazinyl, or NZ¹ orNZ² each also represent 1,4-piperazinediyl, L² is a radical of theformula

where Z³, Z⁴, Z⁵ and Z⁶ are each independently of the others hydrogen,C₁-C₆-alkyl or phenyl, L⁴ is C₂-C₈-alkylene or unsubstituted orC₁-C₄-alkyl-, C₁-C₄-alkoxy- or hydroxysulfonyl-substituted phenylene,and X is in each case as defined above.
 2. The method of claim 1,wherein L³ is a direct bond.
 3. The method of claim 1, wherein A¹ ishydroxysulfonyl.
 4. The method of claim 1, wherein A² is hydrogen orhydroxysulfonyl.
 5. The method of claim 1, wherein L¹ is an azo bridge.6. The method of claim 1, wherein L¹ is a bridge member of the formula

in case 2).
 7. The method of claim 1, wherefor Y is vinyl or a radicalof the formula C₂H₄OSO₃H.
 8. A cosmetic composition, comprising at leastone hair dyeing assistant and one or more dyes of the formula I:

wherein a is 1 or 2, b is 0 or 1, Y is vinyl or a radical of the formulaC₂H₄Q, where Q is an alkali-detachable group, L³ is a direct bond or abridge member of the formula CO—NH—M¹, where M¹ is C₂-C₆-alkylene withor without interruption by 1 or 2 unadjacent oxygen atoms, imino orC₁-C₄-alkylimino groups, A¹ is hydroxysulfonyl or a radical of theformula SO₂Y, A² is hydrogen, hydroxysulfonyl, methoxy, chlorine,bromine or carboxyl, W is either in case 1) the radical of a couplingcomponent, of a monoazo dye or additionally, when b=0, of a disazo dye,which may each bear further fiber-reactive groups, or in case 2) theradical of a chromophore which optionally has further fiber-reactivegroups and is derived from an optionally metallized mono- or disazo dye,from a triphendioxazine, from an anthraquinone, from a metallizedformazan or from a metallized phthalocyanine, L¹ is either in case 1) anazo bridge or in case 2) a bridge member of the formula O₂S—NZ¹, OC—NZ¹,Z¹N—SO₂, Z¹N—CO, Z¹N—CO—NZ², NZ¹ or

where M² is a direct bond or methylene, Z¹ and Z² are each independentlyof the other hydrogen, C₁-C₆-alkyl or phenyl and X is fluorine, chlorineor bromine, amino, C₁-C₆-alkylamino with or without interruption by 1 or2 unadjacent oxygen atoms, imino or C₁-C₄-alkylimino groups and with orwithout hydroxyl substitution, N-pyrrolidinyl, N-piperidinyl,N-morpholinyl, N-piperazinyl or N-(C₁-C₄)-alkylpiperazinyl, or NZ¹ orNZ² each also represent 1,4-piperazinediyl, L² is a radical of theformula

where Z³, Z⁴, Z⁵ and Z⁶ are each independently of the others hydrogen,C₁-C₆-alkyl or phenyl, L⁴ is C₂-C₈-alkylene or unsubstituted orC₁-C₄-alkyl-, C₁-C₄-alkoxy- or hydroxysulfonyl-substituted phenylene,and X is in each case as defined above.
 9. The cosmetic composition ofclaim 8, wherein L³ is a direct bond.
 10. The cosmetic composition ofclaim 8, wherein A¹ is hydroxysulfonyl.
 11. The cosmetic composition ofclaim 8, wherein A² is hydrogen or hydroxysulfonyl.
 12. The cosmeticcomposition of claim 8, wherein L¹ is an azo bridge.
 13. The cosmeticcomposition of claim 8, wherein L¹ is a bridge member of the formula

in case 2).
 14. The cosmetic composition of claim 8, wherein Y is vinylor a radical of the formula C₂H₄OSO₃H.
 15. The cosmetic composition ofclaim 8, further comprising an aqueous cosmetically acceptable medium,wherein the dye is dissolved in the aqueous cosmetically acceptablemedium.
 16. The cosmetic composition of claim 15, having a pH of 5 to 9.17. The cosmetic composition of claim 8, wherein the dye is present inan amount of from 0.01 to 10% by weight, based on the total weight ofthe composition.
 18. The cosmetic composition of claim 8, wherein theassistant comprises at least one surfactant selected from the groupconsisting of anionic, cationic, nonionic, amphoteric surfactant, and amixture thereof.
 19. The cosmetic composition of claim 18, wherein thesurfactant is present in the composition in an amount of 0.5 to 40% byweight, based on the total weight of the composition.
 20. The cosmeticcomposition of claim 8, wherein the assistant comprises at least oneselected from the group consisting of soaps, alkylbenzenesulfonates,alkylnaphthalenesulfonates, sulfates, ether sulfates of fatty alcohols,ether sulfonates of fatty alcohols, quaternary ammonium salts,trimethylcetylammonium bromide, cetylpyridinium bromide, quaternium 1 toX, cocoyltrimethylammonium methylsulfate, hydroxyethylcetyldimomiumphosphate, cetyltrimethylammonium chloride, optionally ethoxylated fattyacid ethanolamides, polyethoxylated acids, polyethoxylated alcohols,polyethoxylated amines, polyglycerated alcohols, polyethoxylatedalkylphenols polyglycerated alkylphenols, and polyethoxylated alkylsulfates.
 21. The cosmetic composition of claim 8, wherein the assistantcomprises at least one organic solvent selected from the groupconsisting of C₁-C₄-alcohol, ethanol, isopropanol, glycols, glycolethers, ethylene glycol, propylene glycol, 2-methoxyethanol,2-ethoxyethanol, 2-butoxyethanol and glycerol.
 22. The cosmeticcomposition of claim 21, wherein the solvent is present in an amount of0-40% by weight, based on the total weight of the composition.
 23. Thecosmetic composition of claim 8, further comprising at least onethickener selected from the group consisting of cellulose derivatives,methyl-cellulose, hydroxymethyl-cellulose, hydroxyethyl-cellulose,hydroxypropyl-cellulose, carboxymethyl-cellulose, sodium alginate, gumarabic, xanthan gum, tragacanth, acrylic acid polymers,polyvinylpyrrolidone, vinyl acetate/crotonic acid copolymers, vinylacetate/vinylpyrrolidone copolymers, butyl vinyl ether/malefic anhydridecopolymers, methyl vinyl ether/malefic anhydride copolymers, inorganicthickener, and bentonite.
 24. The cosmetic composition of claim 23,wherein the thickener is present in an amount of up to 5% by weight,based on the total weight of the composition.
 25. The cosmeticcomposition of claim 8, further comprising at least one substanceselected from the group consisting of carbomers, cationic polymers,silicone compounds, polyquaternium 1 to x, copolymers ofvinylpyrrolidone/vinylimidazolium salts, copolymers ofvinylpyrrolidone/dimethylaminoethyl methacrylate quaternized withdiethyl sulfate, cationic cellulose derivatives, acrylamido copolymers,cationic guar gum derivatives, guar hydroxypropyltriminium chloride,polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes,polyethersiloxanes and silicone resins.